Cotton-dyes.



, aagi/v ,UNTTED %TATE% PATENT @FFlfiE.

AUGUST BLANK, CARL HEIDENREIGH, AND JOHANNES JANSEN, 01T LEVERKUSEN,NEAR COLOGNE, GERMANY, ASSIGNORS T0 FARBENFABRIKEN VORM. FRIEDR.

BAYER 86 (30., OF ELBERFELD, GERMANY, A CORPORATION OF GERMANY.

No Drawing.

the German Empire, residing at Leverkusen, near Cologne-on-the-Rhine,Germany,

have invented new and useful Improvements in Cotton-Dyes, ofwhich thefollowing is a specification. r We have found that new and valuablecotton dyes can be obtained by combining two molecules of a diazotizedacidyl para diamin with one molecule of the 5.5.-dioxy-2.2-dinaphthylamin7.7-disulfonic acid of the formula:

l l 1,! ll

splitting cit the acidyl radicals, tetrazotizin which R and R. arearomatic nuclei 0. g. of the benzene or naphthalene series, and R and Rare end components containing auxochrome groups in meta position to eachother,

In order to illustrate the new process more fully the following exampleis given, the parts being by weight:30 parts of para-aminoacetanilid arediazotized with 60 parts of concentrated hydrochloric acid (1.16specific gravity) and 13.8 parts of nitrite. The diazo solution is thenadded to a solution cooled to zero of parts of the 5.5-dioxy2.2-dinaphthylamin 7."-disultonic acid (sodium salt) in 1000 parts ofwater and 42 parts of calcined soda. The mixture is stirred during 12hours, heated to 90 C. and kept at this temperature during half an hourafter the addition of 300 parts of a. 33. per cent. caustic soda lye.

' Specification of Letters Patent. Application filed April 1, 1913.Serial No. 758,113:

COTTON-DYES.

Patented Mar. 17, 1914.

ing, and coupling the resulting tetrazo compounds with an azodyestuficomponent contaming one or more auxochrome groups in meta position, a.9. OH or N11,, which enable after-treatment with formaldehyde, such asresorcin, a meta-diamin, meta-aminophenol or their derivatives. The newproducts dye cotton generally blue bright shades. The colors arerendered fast to washing by aftertreatment with formaldehyde of fibersdyed with them. They are after being dried and pulverized in the shapeof their alkaline salts dark powders soluble in water and inconcentrated sul uric acid generally with a blue coloration;

yielding upon reduction with stannous.

chlorid and hydrochloric acid the 6.6- diamino 5.5 dioxy 2.2dinaphthylamin- 7.7-disulfonic acid, a para-diamin and an amin and havina constitution corresponding to the formu la:

Subsequently the mixture is neutralized with HCl and the'dye is saltedout and filtered oil. It is then stirred up with 1500 parts of water,rendered slightly alkaline with caustic soda lye, cooled to 10 (3.,acidulated with parts of hydrochloric acid and 13.8 parts of sodiumnitrite and stirred during 6 hours. To the mixture thus obtained is thenintroduced a solution of 9.2

parts of resorcin in 1000 parts of water containing 60 parts of calcinedsodium carbonate. The mixture is heated to 6070 C.

and the dye is salted out and filtered oil. v

It is after being dried and pulverized in the shape of its sodium salt ablue-black powder soluble in water with a blue coloration, soluble inconcentrated sulfuric acid (66 Upon treatment with stannous chlorid andhydrochloric acid it,is split up, the 6.6-diamino-5.5-dioxy2.2-dinaphthylamin 7 .7 dis'ulfonic acid, para-phenylenediaminand aminoresorcin are obtained. It dyes cotton red-.

Other diamins e. g. 2-oxalylamino-5- amino-para-xylol,2-amino-5-acetylaminotoluene, 2 oxalylamino 4 methyl- 5-aminoanisol,acidyl 1. l-naphthylenediamin-6-sulfonic acid, etc.

Instead of resorcin other components, such which dyes are after beingdried and pulverized in the shape of their alkaline salts dark powderssoluble in water and in concentrated sulfuric acid generally with a bluecoloration; yielding upon reduction with stannous chlorid andhydrochloric acid the 6.6 diamino 5.5 dioxy 2.2 dinaphthylamin 7.7disulfonic acid, a para in which R and R are aromatic nuclei of thebenzene series,'and' R and R end components of the benzene series havingauxochrome groups in meta position to each other which dyes are afterbeingdried and pulverized in the shape of their alkaline salts darkpowders soluble in water and in concentrated sulfuric acid'generallywith a blue coloration; yielding upon reduction with stannous chloridand hydrochloric acid the macaw dish-blue and has in a free state mostprobably the formula SOIH ' NNoHNNClI 'll 4 EI\OH as metaphenylenediamin, metaaminophenol, etc, can be used. Y

We claim 1. The herein described new dyestuffs having a constitutioncorresponding to the formula:

diamin and an amin; and dyeing cotton generally blue bright shades whichare rendered fast to washing by an aftertreat ment with formaldehyde,substantially as described.

2. The hereindescribed new dyestuifs having aconstitution correspondingto the formula:

6.6 diamino 5.5 dioxy 2.2 dinaphthylamin 7 .7 disulfonic acid, a paradiamin and an amin; and dyeing cotton generally bright blue shades whichare rendered fast to washing by an after-treatment with formaldehydesubstantially as described.

3. The hereindescribed new dyestuffs having a. constitutioncorresponding to the formula:

ders soluble in water and in concentrated sulfuric acid generally with ablue coloration; yielding upon reduction with stannous chloridandhydrochloric acid the 6.6- diamino 5.5 dioxy 2.2 dinaphthylamin 7.7disulfonic acid, a para diamin and an amin; and dyeing cotton generallybright blue shades which are rendered fast 4. The herein described newdyestutt havto Washing by an after treatment With foring in a free statemost probably the for 5 Inaldehyde, substantially as described. mula:

which is after being dried and pulverized in In testimony whereof wehave hereunto the shape of its sodiuni salt a blue-black set our handsin the presence of two sub- 20 powder soluble in water with a blue andin scribing Witnesses.

concentrated sulfuric acid (66 with a I a 1 blue coloration; yieldingupon treatment AUGUST BLANK. [n.s

with stannons ehlorid and hydrochloric acid i CAR-L HEIDENREICH. [L 5:]the 6.6 diarnino 5.5 dioxy 2.2 di- JOHANNES JANSEN. [L.s.]

nag lhtl'iylamin 7.7 disulfonic acid, para phenylenediainin andamino-resorcin; and dyeing cotton blue shades, rendered fast to washingby an aitertreatment with formaldehyde, substantially as described.

Witnesses HELEN NUrEn, Dona NUrEn.

it is hereby certified that in Letters Patent No. 1,090, 379, grantedMarch 17, 191 C5? upon the application of August Blank, Carllleldenreleh, and Johannes Jansen, of 2: LQVQI'RUSCI'I, near Cologne,Germany, an error appears in the printed specification 5 rerntiringcorrection as follows: Page 2, second torlnula, tor can I 2 so-,I-i

U) 1 a. road i l i 1 1 l y CD R *l\:l\-RN=I\ I\=N-,R -N=NL3 a:

G3 I l ...J OH on and that the said Letters Patent should be read withthis correction therein that g the same may conform to the record oi theease 1n the Patent Olliee.

Correct Signed and sealed this 12th day of May, A. D., 191%.

[SEAL] i i J. T. NEWTON,

Action] Commissioner of Patent-

